Conversion of acyloxymethylene-4-pentenoates to ether esters



Patented Jan. 8, 1952 UNITED 1 2,582,212 PATENT OFFICE- CONVERSION OF: A'CYLOXYMETHYLENE-4 1 PENTENOATESITO ETHER ESTERS' 1011111 Van H0ok,, P-hiladelphia, and Willard J Croxall', Bryn Athyn, Pa., assignors to Rohm & Haas" Company; Philadelphia, Pa., a corporation of Delaware No- Drawing;

wherein R is a phenyl group; an alkyl' group of T not over "four "carbon atoms; hydrogen; chlorine; orbromine, R -is likewise-hydrogen, chlorine; bromine, an alkyl group of not over four carbon atoms, or a phenyl'group'; and B is -a=nontertiary hydrocarbon'group particularly an alkyl group of.not over eight carbon atoms joined to oxygen at a" non-tertiary 'carbomatom, are-rearrangedfby heating at 150"to 250 C; to yield compounds of the formula HO on=o o 0 012+,

ta (JHL It is." also shown-in.fthe eaboveeidentified-iapplica-= tion in? application Serial 1 No. 72,075,. filed on even date now PatentflNon 2,540,070; that the freehydroxyl group-of therearrangedv compounds, reacts; with. acid anhydrides toyield r. acyloxy,v derivatives. Wehavenowdiscovered thatthese derivatives reactwith alcohols in the presence of .an acidic. catalyst to- :yieldether esters oi the-- formula:

R0CH;:G-C '0 0m (01' .R) I

where"R"is a' hydrocarbon residue of a'nonn tertiary" alcohol of not over eighteen carbon atoms, R..OH.- It is a preferred condition that- RP'contain not over nine carbon atoms; The claims of thepresent application are directed to the'above ether-ester-and to the process of their. preparation, particularly where R is'an alkyl'or cycloalkyl group. Thesitua-tion'in which R is'a 2,3-unsaturated'group and the resulting ether is rearranged is shown inour application Serial No. 72,073, now PatentNO. 2,540,073;

The above products are new ether esters which are of considerable interest. Theyhave unsaturated linkageswhich give them chemical reactivity; They areof 'value'in' the'formation ofpolymeric products: They react with ureas and thioureas-to form uracils'and thiouracils. When R has'an allylic structure, the-'new ether esters are rearranged by heating to yield malonaldehydates. Thus, when. Rhas thestructure Application January 21, 1949; Serial No.

11' Clail n's.'- (Cl. 260-468) When this compoundis heated' with: an. alkali. metal hydroxide oraalkoxide; such as potassium hydroxide or sodium alloxide itloses i the". CO9

group from the aldehyde group to iorm'resters of" R representing. 2 ,3'-unsaturated hydrocarbongroups.

The starting materials:- for use-in this invention may be derived from acetyleneanda normal ester'sof" carbonic acid; As'is shown in. applica tion Serial No. 52,607, filed by Croxall i and Schneider on October 2 1948} now Patent No. 2,535,001, acetylene. reacts. with. ester. ofcarbonic. acid' anda nonstertiary alcohol .in..the presenceofan anhydrous, strongly alkaline .cate alyst to form. beta-ether -.acrylates andbetaubeta: diether propionates,v When diallylvcarbonate. is. used, there are .obtainedallyl beta-alloxyacrylata and.ally1 beta,beta,-di(alloxy) propionate. Other carbonates may be. used-in place offallylicars bonate, both saturated. and..unsaturated-. In place of the allyl group proper, there may be used other 2,3-unsaturated alcohol residues."

It is-lnot necessary, however, toh priepare at .this Y stage. anether esterhavingl allylic? groups... The

starting.,.carbonate. ester. may, be. thatroi. alower? saturatedaliphatic alcohol; ROH,.. such as:di.-. methyl. carbonate, diethyl carbonate. dipropyl carbonate. or dibutyl carbonate" These react with acetyleneflbetween 10? C. andillo? C. in the presence. of an-alkaline catalystto .give .corresponding, beta-alkoxyacrylate: and; beta,beta.f dia-lkoxypropionates. When-such an. ether. ester. is heated. with a 2,3-.-unsaturated. alcohol,. R;iOH,.. in thepresenoe of analkalinecatalyst, thelower.

. alkyl groups are displacetLby, the: unsaturated.

alcohol residue, as fallswithin the-purview. of application Serial. No. 52,601, filed.v by Croxall and Van. Hooklvon October 2, 1948; now Patent No. 2,535,009.

Boththe. ether andtheestergroupings needv not, however,- be. thus replaced The -alkyl. group. forming. the .etheriunction may be selectively re. placecLwith .anotheralcohol residue. Thisiaaocomplished by. heating an.- alkyl beta-.alkoxyacrylateor. alkyl beta-,beta-dialkoxypropionatev with an alcohol .ROI-I,v which boils higher, than..- ROI-Iandwhich is.:hereunsaturatedain the 2,3: position, in, the presence of..a.. mildly acidic: cata: lyst, such. as..an..alka1i..metal. sulfate.v Thereisl taken. from the. reaction-mixture thealcohol cor:

terrupted. In this way ether esters of the formulae R'OCI-IzCHCOOR and (R'O) 2CHCH2COOR are obtained as is more fully described in application Serial No. 52,602, filed by Croxall and Van 7 Hook on October 2, 1948, now Patent No. 2,535,010.

The beta,beta-diether propionates are converted to beta-monoether acrylates when the former are heated in the presence of a dealcoholating catalyst, such as an alkali metal acid sulfate or an alkali, and a mole of alcohol taken off per mole of ester. This process is described in detail in application Serial No. 52,608, filed by Croxall and Schneider on October 2, 1948, now Patent No.

The most convenient and economical method for introducing one of these groups is through transetherification of an alkyl beta-alkoxy acrylate or beta,beta-dialkoxypropionate by methods shown above. A mixture of alkyl betaalkoxyacrylate and alkyl beta,beta-dialkoxypropionate may be used quite as well as the individual ether esters. There are thus obtained compounds of the formula where R. under these conditions is an alkyl group of not over eight carbon atoms, particularly an alkyl group of one to four carbon atoms, and E and B. have the significance described above. ,It is necessary that during transetherification the reaction temperature be maintained below 150 C. if the above compounds are to be isolated. For this purpose the alcohol ROI-I, which is displaced, is advantageously taken off under re duced pressure. If isolation of a transetherified etherester is not required, the reaction may be carried over this stage and only the rear ranged products isolated.

One may thus start with an ester, (R+O)2CO, of carbonic acid and of a saturated monohydric alcohol, R+OH where R+ is a non-tertiary hydrocarbon group, particularly an alkyl group of not over eight carbon atoms and preferably not over four carbon atoms. By reaction thereof with acetylene at C. to 110 C. in the presence of a strongly alkaline catalyst such as an alkali metal acetylide, an alkali metal alcoholate, or a strongly basic quaternary ammonium alkoxide, there are obtained such acrylates as methyl betamethoxyacrylate, e t h y l beta-ethoxyacrylate, propyl beta-propoxyacrylate, butyl beta-butoxyacrylate, hexyl beta-hexoxyacrylate, or octyl beta-octoxyacrylate, or such propionates as methyl beta,beta'-dimethoxypropionate, ethyl beta, beta diethoxypropionate, butyl beta,beta-dibutoxypropionate, or octyl beta,betadioctoxypropionate, or mixtures of ether acrylate and diether propionate. Esters such as allyl beta-alloxyacrylate or betaJceta-dialloxypropionate may likewise. be made. Along with these there may be obtained ether maleates and diether succinates.

When acetylene is no longer absorbed by the reaction mixture, the catalyst is destroyed and thereactionmixture separated by distillation. A fraction containing ether acrylate and diether propionate may be taken off. This may be heated, desirably under reduced pressure, with an alkali metal acid sulfate and the propionate-decomposed to acrylate, although this is not .essential. I

The alkoxy acrylates may then be transetherifled by heating them with a 2,3-unsaturated alcohol, R'OH, such as allyl chloroallyl, 3-chloroallyl, 2-bromoallyl, 2-methallyl, 2-ethallyl, 2- butallyl, crotyl, or cinnamyl alcohol or Z-pentenol, 2-hexenol, or Z-heptenol. A mildly acidic catalyst is used at concentrations of 0.01% to 1% of I the weight of the ether ester. The alcohol ROH is displaced at temperatures between C. to C. at normal or reduced pressures. permits isolation of the compound where R is the unsaturated group introduced.

This product is then heated at 150 C. to 250 C., preferably 150 C. to 200 C., and is thereby re arranged. The resulting ester of 2-hydroxymethylene-4-pentenoic acid may then be separated, if desired.

Alternatively, the same ester may be obtained by heating an alkyl beta-alkoxyacrylate or beta, beta-dialkoxypropionate at 150 C. to 250 C. in the presence of an alkali metal acid sulfate with a beta,gamma-unsaturated alcohol, R'OH. Transetherification and rearrangement both occur. The alcohol displaced is distilled ofi, the catalyst is destroyed, and the rearranged product is isolated.

Similarly, an alkyl beta-alkoxyacrylate is heated at 150 C. to 250 C. in the presence of an alkaline catalyst with an alcohol having a hydrocarbon residue olefinically unsaturated in the beta,gamma-position. Transetherification and transesterification now both take place accompanied by rearrangement of one unsaturated group introduced from the beta,gamma-unsaturated alcohol. Under these conditions there can be separated transetherified and transesterified acrylates and also esters of 2-hydroxymethylene- 4-pentenoic acid. If heating is prolonged or continued at elevated temperatures, there may even occur decarbonylation of the last-named esters to -pentenoates.

There follows a description of the preparation of specific intermediate compounds in order to 7 illustrate the procedures which have been generally set forth above.

A; In a reaction vessel equipped with a packed distilling column there were mixed 500 grams of ethyl beta-ethoxyacrylate, which had been prepared according to the procedures detailed in ap-- This beta-naphthcl as a polymerization inhibitor, was 10.

stirred and heated at 150 C. C.) for two hours. It was then cooled to 10 C. and mixed with a solution of 80 grams of sodium hydroxide imfzllfl m-l. of;:Wate r,;ia-1'So.,ahiIQf C. Thisimixture was.allowedztcrormdayera whi havere.s paratede.

The aqueous:layeriwasextracted: with e hyl ether-. The ether-extract WaS:'CQi11biI1d:..V /.ith; theior emc;v y r. Y the: .ethercevaporated; and nreaetedre h lli betaealloxyaerylatel. newreared:= y: ist llation..- The :aqueeus. layerzwas; 1 endered acidic; tion; of; hydrochloric; dildo. an: crga-niczrleyerr thEIZEUDODLWaS; formed-1. ltfwas eparated: from. thiezaiillfious. layer-by.zextractior with ethylze her: Theetherz-oreaniclayenzwas dr. d Meta-cal ium;

sulfata drying: agent. lldii distill d:- After:- the:v

ether:had:beennstrippedaoifzc.there;ww btaineda a-fractionofz9b,gramsdi illinglzatlfi3fi -76 [2;5' m-m.,.and: corresponding:-jmcomposition;;to ethyl 2-hydroxymethylenee ltperrtenoatez. This; subg. stance.was.redistilledat l'lt C'.'/-l mm.

In: the; aboveedescribed; preparation but one. allyla-group was introduceddI-r the-aetlienaclfyl by; transetherificatien. BQthr: transetherififi'... tionzand-"transesterificatiommamx however. be fir fected toxintroduce.twaallizliearoups; as 35,

bGTShOWILL. 1

There; were}: mixedc in; a: reaction vessel? equipped with a... paclteds distilling column lei-t grams of ethyl betaeethoxyacnylatea.175:; grams; of methallyl alcohol in which live grams otsotlium. had been dissolved, and 200 grams of toluene. The mixture was heated and an azeot ope of ethanol and toluene taken oiT at 76 t0-;85' C. while the pot temperature gradually rose to 125 C. The charge was cooled, poured into water, and acidified. An oil layer formed which was a separated, Washed with brine, dried, and distilled. After toluene had been removed, most of the remaining liquidwasdistillcdbetweenF103 and 1e05, C./1 mm. It was washedwith 200 ml. of a cold aqueous solution containing 10% of sodium hydroxide. The organic layer was separated-{dried over anhydrous potassium carbonate, and; distilled. There was obtained 12 grams of methallyl l-methyl-4-pentenoate at, 32-40 -C./t 42 grams of methallyl beta methalloxyacrylate at 40 to 85 C./1 and'2'7i grams of methail-yl beta;beta.-.di;(methalloxy)propionate at 8.5% tc .90.v C./1 mm.

D. The methallyl beta-methalloxyacrylate was 2-hydroxymethylene-epentenoieacidand ofsat-- These react. witlrcarb ylic.acidjanliydndes. such. as.a..,c et ic:anh .de...prcpionican y r de;plume., anhydrice, or th liketo form ea yloxyder ra tires R"ooooH-=oj ooo1r o 1y ome "R11: It em wh reR is; preierablyean alkyl. .e rciip t.nqt:even. h'ree carbonatoms-i. Fonthisreacti n.the st r of. yd o-Xymethyl-- ene-4 pentenoic. acid. andacid. anhydride; are mixed. After-.- the initi.al..r a ti0nha isubs dedt th re may bedisll z led iron-th .react qnmix ure th marboxyl-ic acid... crm d,as a byproduc -M Thea acylatedester; remains :and may be used in ,this, form or.may;.be, purified, as by. distillation The. f llowi rep cifi xampl s llus ra ng his. procedure. E. A mixture; of.15'-7 ..grams-0f..ethyl ,2,-.hydroxy;.. methylene aepentenoate and..22.0 grams o f,aceticv anhydride was heated in a... reaction, vesseli equipped with a distillin column. Acetic acid was taken ofi at to C. whereupon a mixture of acetic acid and acetic anhydride wasrqb'e. tamed; 'Iihegreactibrrzmixturawasmhemdistined underrreduced pressurei. Ai ee: he-:: e anhydridehad ;been=- ta en ofi,1the rewa tion. f. butyrieranhrdridesforzaeetie:on prep omc:

anhydride led to ethyl 2-butyroxymethyleneg4t pentencata; I

An; alternative approach;v to; the acy'lated; l est isebye-heatingamalloxycrylat with aicarboxyl-i acickranhydride. Theoretically ,=.the; Zrh $rmethylene z-.4t-pentenoategisaformedy;andracylated In any; case theslproducti. separated; is: a; beta':= a yloxymethy rreeeepenteneate.:.

G's. As;illustnativeeot hi :lastmethod; theefclm lowineza ee n f. ztypicai prepar tiomiisgive e.

A mixture of 197 grams of ethyl beta-allergy acrylate and 255.. grams, oiacetic anhydride of 90% -purity was heated to C. in a flask equipped with a, four-foot packed column. There was taken oil a small-amount of material at overhead temperatures oi 60 to 115 C. There was then obtained at 118-125 C. '76 grams of acetic acid whilelthen t. temperature ad anee to 7 he pressure. w thiuthie.app at s a th n. reduced...andiexcessacetie anhxdr cle ken o The remainin material was, .subjected. to Iraqtionaljdistillation at; reduced pressure, After a small forerun a fraction amounting to 17'0 gramswas obtained atf102-1'08- Q./2-3,mm. It had'ag; refractive-index', n of-IAGOQ; a molecular 're fraction, MR of 5'-1.41 and a density;

20 20: of 1.056; It had a saponificatiorrnumber. 01 563? and ianacidanumber. .oj.. 23;4-:l Itmontained 59.36%,

01 carbon and 7.33% of hydrogen. These values agree well with those calculated for ethyl 2-acetoxymethylene-4-pentenoate, for which theoretical values are saponification number568, acid numbar-284, ME -50.76, carbon content-60.59%, and hydrogen content--7.12%.

In place of acetic anhydride in the above specific examples, there may be used other carboxylic acid anhydrides to give the corresponding 2-acyloxymethylenel-pentenoates such as ethyl 2-propionoxymethylene-4-pentenoate and ethyl 2- butyroxymethylene-4-pentenoate. In place of the ethyl ester, there may be used other esters, such as methyl, propyl, butyl, hexyl, or octyl, or an alkenyl group, such as 'allyl, methallyl, crotyl, cinnamyl, chlorallyl, bromallyl, or the like.

H. A mixture of 156 grams (1.0 mole) of ethyl beta-alloxyacrylate and 195 grams (1.5 moles) of propionic anhydride was heated in a Claisen flask at 1721'75 C. while 79 grams (1.0'7 moles) of propionic acid was distilled off at 133-140 C. This had a refractive index, 12 of 1.3920. The residue was cooled and the distillation was continued in vacuo. After excess propionic anhydride was distilled ofi at 3589 C./0.5 mm. in an amount of 92 grams, there was obtained 140 grams (66% yield) of ethyl 2-propionoxymethylenel-pentenoate which distilled at 899'7 C./ 0.5 mm. On redistillation, it boiled at 92-94 C./0.5 mm. and had an index of refraction, n of 1.4597 and a density,

I. A mixture of 156 grams (1.0 mole) of ethyl beta-alloxyacrylate and 237 grams (1.5 moles) of butyric anhydride was heated in a Claisen flask at 179202 C. while 94 grams (1.07 moles) of butyric acid which distilled at 135154 C. was collected. The residue was cooled and the distil lation was continued in vacuo. After removal of 128 grams of butyric anhydride, which distilled at 4695 C./0.5 mm., there was obtained 125 grams (52% yield) of ethyl Z-butyroxymethylene- -pentenoate which distilled at 95-102" C./0.4 mm. and had an index of refraction, n of 1.4571.

Since the acyloxy group is to be displaced according to this invention, there is ordinarily no advantage in the use of other than the smallest and most economical group, the acetoxy group, in forming the 2-acyloxymethylene substituent. This invention is directed to the replacement of the acyloxy group, specifically the acetoxy group, and conversion thereof to an alkoxy group. This is accomplished by heating an ester of the formula with an alcohol, R OH, in the presence of an acidic catalyst. Temperatures of 50 to 150 C. or more may be used. Suitable catalysts are phosphoric acid, sulfuric acid, p-toluene sulfonic acid, or other acid which is effective in esterification reactions. The acyl group is removed through formation of an ester with the alcohol, or with the alcohol group from the original 2-acyloxymethylene-4-pentenoate ester, or both. The ester, R"COOR or R 'COOR is removed by volatilization, under reduced pressure if advantageous. The ester-forming group, R, may also.

8' be replaced with R and the alcohol ROI-I taken off. The product obtained is of the formula R1 AH:

R0CH=CCOOR H R1 ()Rfl Hz The alcohol, R OH, which is used for this operation may be any non-tertiary monohydric alcohol. Particularly suitable are those primary and secondary alcohols in which the residue R" is a hydrocarbon group, acyclic or alicyclic, including alkyl or cycloalkyl groups, such as butyl. isobutyl, sec.-butyl, hexyl, z-ethylbutyl, isoheptyl, octyl, capryl, decyl, dodecyl, cetyl, stearyl, cyclohexyl, methylcyclohexyl, or the like, and groups such as benzyl, methylbenzyl, hexahydrobenzyl, hydroterpenyl, etc. Unsaturated hydrocarbon groups, such as allyl, crotyl, cinnamyl, methallyl, ethallyl, propallyl, hexenyl, undecyl, oleyl, tetrahydrobenzyl, terpenyl, endomethylenetetrahydrobenzyl, etc., are also of considerable interest, as they give particularly useful and reactive derivatives. When R is a 2,3-unsaturated alcohol residue; i. e., an allylic alcohol (ROH), ethers of hydroxymethylene-4-pentenoates are obtained which undergo an allylic rearrangement, whenheated, to form new unsaturated aldehydo-carboxylates or malonaldehydates. These lose their aldehyde group when heated withan alkali hydroxide or an alkali metal alcoholate. Thus, when R has the structure HCR =C(R*)CHz-, the following reactions can occur The following examples are illustrative of the process of this invention which is here claimed.

Example 1 A mixture of 60 grams of ethyl Z-acetoxymethylene-4-pentenoate, ml. of methanol, and one gram of p-toluene sulfonic acid was heated in a reaction vessel carrying a distilling column. Methyl acetate was distilled therefrom at temperatures of 56"--64 C. Excess methanol was taken ofi and the reaction mixture subjected to distillation under reduced pressure. There was obtained at 55-67 C./ 1 mm. ethyl Z-methoxymethylene-ei-pentenoate in an amount of 2'7 grams. The refractive index, 12, was 1.4633.

, Example-2 A mixture of 104 grams o'fethyl 2=acetoxymethylene '4=pentenoate, 150 grams. of ethanol (anhydrous), and one gram of p-toluene sulfonic acid was heatedin-a reactionvessel equipped with a four-foot distillingcolumn. There was taken acetate. The remaining liquid was fractionated through a packed column under reduced pressure. There wasobtained 71 grams of ethyl 2- ethoxymethylene-4-pentenoate, distilling at 65- "70 "1 0.704 mm; having a refractive index, 11. of 21.4644, and containing :by "analysis 65.46% of carbon f'and 8.72% of "hydrogen. "Theoretical fll-ie'xanol, 1 and a half gram "of sulfuric acid was heated in a reaction vessel e'quippe'ctwith dis- :t'illing column. At =68'-70 'C. (overhead) there was"taken-' on ethyl acetate. When: the-pot temp'er-at'ure reached 190 C., distillation under reduced-"pressure wa's resorted to. At48 80 C'./0-.2

grains of a mixture of- 2 ethylhexylacetate and 2-ethylhexanol was distilled-out. There grams of a mixture of 2 ethylhexyliacetateand 2' ethylhexyl 2 -i(2 ethylhexoxymethylene)-4 pentanoate. This mixture had a refractive index of 1.4540. At 128-190 C./0.2 mm. there was obethylhexoxymethylen'e) 4pentenoate, -'ainounting to 147 grams,'"havinga"refractive index of 1.4660. This product wasredistilled at 158-176 C./0.5 mm. It-then had a refractive index, n

of 1.4658 and had a saponification equivalent of "360. The theoreticarnuinber is 352.

:Exa'mp'le 4 A mixturecf 100 grams 'of ethyl Z-acetoxymethylene-4epentenoate, 200 grams of cyclohexanol, and two grams of. phosphoric acidwas heated in a reaction vessel carrying'a "shortdistilling column. At 58-79 C. there was obtained in an: amount of 45 grams ethyl acetate. When the pot temperature reached 164 C., distillation under reduced pressure was used. At 45-57 C./1 mm. 105 gramsrofcyclohexanol was taken off. At 1l8to 152C./1-2 mm. 71 grams of cyclohexyl 2-cyclohexoxymethylene-4-pentenoate was obtained with slight decomposition occurring in the pQt-asshQWn-byevolution of gas. The product-was redistilled at 140-144 C./0.2 mm. It then had a refractive index of 1.5025 and a sapomfication'equivalentof 300 (theory is 292).

In place of .the ethyl ester. of Z-acyloxymethylene4-pentenoic "acid'used above, there may be used in place of the ethyl group the methyl, propyl, biityl-, amyl, hexyl, heptyl oroctyl group withlsimilar results. It'will-be notedthat the alcohol residue of the starting'ester maybe-replaced during .the reaction. When the ester-- forming group is'thus' replacd with the residue R., it is, of course, desirable that the -;original ester have .onlya small-alcohol residuetas the ester-forming group, such as methyl idr ethyl. Hence, methyl or .ethyl 2-acetoxymethylene-4- ,pentenoates are preferred as starting materials.

Thereaction of a 2,-3-unsaturated alcohol of .the-form'ula U v R -CH -C (R1 C-I-IzOH with an ester l of a 2-acyloxymethylene-4 pen- 5 -tenoate is: a special case; for; as has been 'already indicated, n'ot e'nIyis the: 'ac'yl I group :displac'ed, but a rearrangement of the alloxymethylene group can occur and occurs increasingly as the temperature is raised. Thus, l while the primary group, above 150 C. replacement i's accoinpanied by rearrangement. :When-the rearranged product is that desired, the acyloxymethylene-4-pen- 'tenoate maybeheated with an allylicalcohol at .150? C. to 250 @C. in the presence v of catalyst and .the rearrahgedfproducti separated.

:Ea:ampZe-5 20 mixtureo'f IQO'gra-ms oi'ethyl Z acetOXymethylene=4-pehtenoate, 87 grams or allyl alcohol; one gram of p-toluen'e s'ulfonic' aci'd, and two [grams of beta-naphthol was heated in a' 'reaction "vesselequipp'edwith a distilling column. Abdisallyl'ae'etateand allyl alcohol was obtained. Exce'ss auyra-icchoi was stripped; ofiunder reduced pressure. The re'ii'iaining'liquid'was fractionally distilled. Between' 78and 99 C./1 mm. there was obtained a distillate which was chiefly allyl 2 alloxyrnethylene l pentenoate. i'Between {100 C. and 135 C./1 mm. the distillate wasami'xture 6f allyl diallylrnalona'ldehydateandallyl-2 alloxy- 35 methylene-4-pentenoate. This was heated vto 220 C. and subjected to fractional distillation.

There was obtained at67-68 C./1 mm. or 73-'75 C./2 mm. a liquid, for which 11 was 1.4532,

'was 0.997, and the saponificationequivalent was 5104:. Thisicorresponded in composition to'allyl diallylmalonaldehydate,

CH2G-H=OH: OHC- b-OOOCH;OH=CH =UHzCH=CHz EWh'iChFIGQllll'B-S two moles of-alkali for complete reaction, since-the ester is saponified-andthe-alrdehyde group -is cleaved to yieldiormate. in .-;place of'the allyl alcohol shownabova there may .be used: chlcrallyl, ibrornoallyl, crotyl, -3 -et hally1, 1:3-butal1yl, or-cinnamylalcohols. In everycase ,the g-acyl group is displaced and .a new; ether formed, which-undergoes rearrangement. When ,theyallylicfgroupris hydrocarbon, the malonaldehydate yields, when heated with alkali,. such as potassium hydroxide or a sodium alcoholate, allyl diallylacetate and potassium or sodium formate.

Example 6 ,A. mixture .gfifos grams (0.5- male) or ethylf2- q propionoxymethy-lne 4Qpentenoate, ,108 jig'rams (1.5 moles) zofcrotyl alcohol, and 1,. gra'mtf ptoluene sulfonic acid washeated under a two-foot column. There was obtained on distillation a mixture of 9 grainsofwaterand 50 grams of ethyl propiohate, which distilled at '75100 C. while the.pot-..temperature rose from 100 C. to

..:s'tripped .under reduced pressure. The residue was heated at220 for l 5 minutes, cooled, and {then distilled from a Claise'n flask .i'n team. There wasqobtainedfo grains of ,crdtyl allyl; 1- flamthallyl) malonaldeliydate which boiled atI- '90 C./2mm. The residue which consisted of a heavy tar weighed 51 grams. Onredistillation the product boiled at 82-85 C./2 mm., had an index of refraction, n of 1.4492, and gave upon analysis a saponification equivalent of 115.

, Crotyl allyl-(l-methallyl) malonaldehydate calculated as a dibasic acid ester has a saponification equivalent of 118. The 60 grams of product represents a yield of 51%.

Example 7 A solution of 20 ml. of anhydrous ethanol containing one gram of dissolved sodium and 23.6

the theoretical saponification equivalent is 208.

We claim: 1. A process for preparing a compound of the formula ROCH=OCOOR bHzCH cHa which comprises reacting by heating together at 50 to 150 C. in the presence of an acidic catalyst 'from the class consisting of sulfuric acid, phosphoric acid, and p-toluenesulfonic acid a compound of the formula with an excess of a non-tertiary alcohol ROH, separating from the reaction mixture an ester of the acid R"COOI-I, and forming said compound, R." being an alkyl group of not over three carbon atoms, RP being a non-tertiary hydrocarbon group of not over nine carbon atoms, and B being a non-tertiary alkyl group of not over eight carbon atoms, the alcohol ROH boilin at least as high as the alcohol ROH.

2. A process for preparing a compound of the formula which comprises reacting by heating together between 50 and 150 C. in the presence of an acidic catalyst from the class consisting of sulfuric acid,

phospheric acid, and p-toluenesulfonic acid a j compound of the formula with an excess of non-tertiary aliphatic alcohol "7 R OH, separating from the reaction mixture an ester of the acid R"COOH, and forming said compound, R" being an alkyl group of not over three carbon atoms, R. being a non-tertiary aliphatic'hydrocarbon group of not over four carbon atoms olefinically unsaturated in the 2,3-position,

and R being a non-tertiary alkyl group of not 1 over two carbon atoms.

3. The process of claim 2 wherein R9 is the group CH2=CHCH2- 4. A process for preparing a compound of the formula ROCH=CCOOR H2CH=CHz which comprises reacting by heating together between 50 C. and C. in the presence of an acidic catalyst from the class consisting of sulfuric acid, phosphoric acid, and p-toluenesulfonic acid a compound of the formula R"COOCH=CCOOC7H5 omoH=oH= with an excess oi a saturated monohydric aliphatic non-tertiary alcohol R OH, separating from the reaction mixture an ester of the acid RCOOH, and forming said compound, R" being an alkyl group of not over three carbon atoms and RP being the hydrocarbon residue of said alcohol and containing not over eight carbon atoms. 1

5. The process of claim 4 in which R." is 2- ethylhexyl.

6. The process of claim 4 in which RP is ethyl.

7. A compound of the formula wherein R is a non-tertiary hydrocarbon group of not over nine carbon atoms.

8. A compound of the formula R OCH CC 00R" UH CE=CHz wherein R is a non-tertiary alkyl group of not over eight carbon atoms.

9. A compound of the formula CzHaO CH=C-C O O 02H;-

H20 H=O Hg 10. A compound of the formula czHs O H JH-CH -OCH=CC o oomomouzn 04H Hi0 H=CHa 11. A compound of the formula cyclohexyl0 CH=C-C O Ocyclohexyl mcn=o Hz JOHN o. VAN HOOK. WILLARD J. CROXALL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,406,590 DAlelio Aug. 27, 1946 FOREIGN PATENTS Number Country Date 13,347 Great Britain Aug. 31, 1905 of 1905 OTHER REFERENCES Meyer: Comptes Rendus, vol. 203, pp. 1074-1077 

7. A COMPOUND OF THE FORMULA 